JP2016166365A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in rigidity and impact resistance, and a manufacturing method therefor.SOLUTION: There is provided a thermoplastic resin composition containing a polyamide resin in a polyolefin resin in a dispersed manner and obtained by melting and mixing a mixed resin in which the polyamide resin and a compatibilizer are melted and mixed and a polyolefin resin. The compatibilizer is a modified elastomer where a reactive group capable of reacting with a polyamide resin is added to an elastomer (for example an olefin-based thermoplastic elastomer, a styrene-based thermoplastic elastomer, and the like). There is provided the thermoplastic resin composition where the elastomer is olefin-based thermoplastic elastomer consisting of a polymer of ethylene or propylene and α-olefin having 3 to 8 carbon atoms or a styrene-based thermoplastic elastomer.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition and a method for producing the same. More specifically, the present invention relates to a thermoplastic resin composition having excellent rigidity and impact resistance, and a method for producing the same.

2. Description of the Related Art Conventionally, polymer blends (including polymer alloys) in which resins having different polarities are mixed to modify the properties of the resin have been actively studied (see, for example, Patent Documents 1 and 2).
At that time, if the compatibility between the resins is insufficient, the mechanical properties such as impact resistance properties are reduced, and the modification effect by the polymer blend may not be obtained. It is necessary to improve compatibility. For example, in the case of a polymer alloy of a polypropylene resin and a polyamide resin, a method of using a compatibilizing agent such as maleic anhydride-modified polypropylene has been proposed in order to improve the compatibility.

JP 2007-297441 A JP 2009-203410 A

In the fields of automobile interior parts and exterior parts, high mechanical properties are required, and it is indispensable to satisfy both impact resistance and rigidity (flexural modulus).
However, in the above-mentioned polymer blend, the impact resistance characteristics and the rigidity characteristics are in a trade-off relationship with each other, and in particular, there is a conflicting relationship that the rigidity is insufficient by utilizing the impact resistance characteristics. However, the present situation has yet to be obtained that sufficiently satisfy the characteristics of both.

  This invention is made | formed in view of the said situation, and it aims at providing the thermoplastic resin composition which is excellent in rigidity, and is excellent also in an impact-resistant characteristic, and its manufacturing method.

In order to solve the above problems, the invention described in claim 1 is a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin, and the polyamide resin and the compatibilizer are melt-kneaded. The obtained mixed resin and polyolefin resin are obtained by melt-kneading, and the compatibilizer is a modified elastomer in which a reactive group capable of reacting with the polyamide resin is added to the elastomer. To do.
The invention according to claim 2 is the olefin-based thermoplastic elastomer or the styrene-based thermoplastic, wherein the elastomer is a polymer of ethylene or propylene and an α-olefin having 3 to 8 carbon atoms. The gist is that it is an elastomer.
The invention according to claim 3 is a method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin, wherein the polyamide resin and a compatibilizer are melt-kneaded and And a polyolefin resin, and the compatibilizer is a modified elastomer in which a reactive group capable of reacting with the polyamide resin is added to the elastomer.

According to the thermoplastic resin composition of the present invention, since it is obtained by melt-kneading a mixed resin in which a polyamide resin and a specific compatibilizer are melt-kneaded and a polyolefin resin, it has excellent rigidity. Excellent impact resistance.
Further, when the elastomer is an olefinic thermoplastic elastomer composed of a polymer of ethylene or propylene and an α-olefin having 3 to 8 carbon atoms, or a styrene thermoplastic elastomer, more excellent impact resistance and rigidity are obtained. can get.
According to the method for producing a thermoplastic resin composition of the present invention, since a mixing step of melt-kneading a mixed resin in which a polyamide resin and a specific compatibilizer are melt-kneaded and a polyolefin resin is provided, rigidity is increased. And a thermoplastic resin composition having excellent impact resistance can be easily obtained.

It is a graph regarding Charpy impact strength. It is a graph regarding Charpy impact strength. It is explanatory drawing explaining the dispersion state of resin by SEM observation.

  The items shown here are for illustrative purposes and exemplary embodiments of the present invention, and are the most effective and easy-to-understand explanations of the principles and conceptual features of the present invention. It is stated for the purpose of providing what seems to be. In this respect, it is not intended to illustrate the structural details of the present invention beyond what is necessary for a fundamental understanding of the present invention. It will be clear to those skilled in the art how it is actually implemented.

[1] Thermoplastic resin composition The thermoplastic resin composition of the present invention is a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
Obtained by melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin,
The compatibilizing agent is a modified elastomer in which a reactive group capable of reacting with a polyamide resin is added to the elastomer.

(1-1) About Each Component The “polyamide resin” is a polymer having a chain skeleton formed by polymerizing a plurality of monomers via an amide bond (—NH—CO—). The thermoplastic resin composition according to the present invention is a resin that forms a dispersed phase with respect to a polyolefin resin described later.

  Examples of the monomer constituting the polyamide resin include aminocaproic acid, aminoundecanoic acid, aminododecanoic acid, amino acids such as paraaminomethylbenzoic acid, and lactams such as ε-caprolactam, undecane lactam, and ω-lauryllactam. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Furthermore, the polyamide resin can also be obtained by copolymerization of a diamine and a dicarboxylic acid. In this case, the diamine as a monomer is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, , 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1, 16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, 2-methyl Aliphatic diamine such as -1,8-diaminooctane, cyclohexanediamine, bi - (4-aminocyclohexyl) cycloaliphatic diamines such as methane, aromatic diamines such as xylylenediamine (p- phenylenediamine and m- phenylenediamine and the like). These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Furthermore, as the dicarboxylic acid as a monomer, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, Aliphatic dicarboxylic acids such as tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid Etc. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, the polyamide resin is preferably a polyamide resin containing an amide bond-containing unit having 11 carbon atoms in the main chain. That is, a polyamide resin containing a structural unit derived from a monomer having 11 carbon atoms is preferable, and a polymer using 11-aminoundecanoic acid or undecane lactam as a monomer (hereinafter referred to as this heavy polymer). The coalescence is also referred to as “PA11 resin”. In particular, 11-aminoundecanoic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutral).
It is preferable that the structural unit derived from the monomer having 11 carbon atoms is 50% or more of all the structural units in the PA11 resin. That is, a structural unit derived from a monomer having a carbon atom number of less than 11 and / or a structural unit derived from a monomer having a carbon atom number of 12 or more are all structural units in the PA11 resin. It can contain less than 50% of them. Further, the PA11-based resin may be a structural unit derived from a monomer having all the structural units of 11 carbon atoms. That is, the polyamide resin may be polyamide 11 (PA11).

In the present invention, examples of preferable polyamide (A) other than the PA11 resin include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, and polyamide. M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T, polyamide 9T / 2M-8T, and the like.
In addition, these polyamide (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

Moreover, when using together PA11 type | system | group resin and another polyamide, when the whole polyamide resin is 100 mass%, the content rate of another polyamide can be made into less than 40 mass%.
In the polyamide resin, it is preferable that half or more (50% or more) of carbon atoms constituting the main chain constitute a chain skeleton. That is, the polyamide resin may contain an aromatic skeleton, but the number of carbon atoms constituting the aromatic skeleton is preferably less than half (less than 50%) of the carbon atoms constituting the main chain.

  Although the weight average molecular weight (polystyrene conversion) by the gel permeation chromatography (GPC) of a polyamide resin is not specifically limited, It is preferable that it is 5,000-100,000, More preferably, it is 7,500-50,000, Furthermore, Preferably it is 10,000-50,000.

The “polyolefin resin” is a resin that forms a continuous phase with respect to the polyamide resin in the thermoplastic resin composition according to the present invention.
The polyolefin resin is not particularly limited, and various polyolefins can be used. Examples thereof include an ethylene homopolymer, a propylene homopolymer, an ethylene-propylene copolymer, an ethylene-α-olefin copolymer, and a propylene-α-olefin copolymer.
The α-olefin is usually an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and includes propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 3-methyl-1-butene, 4-methyl-1-pentene and the like can be mentioned.
These polyolefin resins may be used individually by 1 type, and may be used in combination of 2 or more type. That is, the polyolefin resin may be a mixture of the above polymers.

  Although the weight average molecular weight (polystyrene conversion) of polyolefin resin by GPC is not specifically limited, It is preferable that it is 10,000-500,000, More preferably, it is 100,000-450,000, More preferably, it is 200,000- 400,000.

  The polyolefin resin is a polyolefin having no affinity for the polyamide resin and a polyolefin having no reactive group capable of reacting with the polyamide resin. It is different from the polyolefin component as an agent.

The “compatibility agent” is a modified elastomer in which a reactive group capable of reacting with a polyamide resin is added to the elastomer.
As the elastomer, a thermoplastic elastomer is usually used. Of the thermoplastic elastomers, olefin-based thermoplastic elastomers and styrene-based thermoplastic elastomers are preferable.

Examples of the olefinic thermoplastic elastomer include those obtained by copolymerization of α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-octene and the like. In particular, a polymer of ethylene or propylene and an α-olefin having 3 to 8 carbon atoms is preferable. That is, a polymer of ethylene and an α-olefin having 3 to 8 carbon atoms and a polymer of propylene and an α-olefin having 4 to 8 carbon atoms are preferable.
Specific examples of the olefin-based thermoplastic elastomer include ethylene-propylene copolymer (EPR), ethylene-1-butene copolymer (EBR), ethylene-1-pentene copolymer, and ethylene-1-octene copolymer. Examples thereof include a polymer (EOR), a propylene-1-butene copolymer (PBR), a propylene-1-pentene copolymer, and a propylene-1-octene copolymer (POR). Among these, EOR, EBR, and EPR are preferable, and EBR and EOR are particularly preferable.

Examples of the styrenic thermoplastic elastomer include a block copolymer of a styrene compound and a conjugated diene compound, and a hydrogenated product thereof.
Examples of the styrene compound include alkyl styrene such as styrene, α-methyl styrene, p-methyl styrene, and pt-butyl styrene, p-methoxy styrene, and vinyl naphthalene.
Examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and the like.

  Specific styrenic thermoplastic elastomers include, for example, styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and styrene-ethylene / butylene-styrene copolymer (SEBS). Styrene-ethylene / propylene-styrene copolymer (SEPS) and the like. Of these, SEBS is preferred.

The reactive group capable of reacting with the polyamide resin includes an acid anhydride group (—CO—O—OC—), a carboxyl group (—COOH), an epoxy group [—C ₂ O (two carbon atoms and 1 A three-membered ring structure composed of two oxygen atoms)], an oxazoline group (—C ₃ H ₄ NO), an isocyanate group (—NCO), and the like. In addition, the method for imparting these reactive groups to the elastomer is not particularly limited, and a known method can be used.

Among the reactive groups described above, an acid anhydride group is particularly preferable. Examples of the monomer for introducing the acid anhydride group include maleic anhydride, phthalic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. And acid anhydrides such as butenyl succinic anhydride. Among these, maleic anhydride, phthalic anhydride, and itaconic anhydride are preferable, and maleic anhydride is particularly preferable.
In addition, these monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, when using the modified elastomer into which acid groups, such as an acid anhydride group, were used as a compatibilizing agent, the amount of acid groups is not particularly limited.

Here, specific modified elastomers used as the compatibilizer of the present invention include, for example, maleic anhydride-modified olefin thermoplastics such as maleic anhydride-modified EPR, maleic anhydride-modified EBR, and maleic anhydride-modified EOR. Examples include elastomers and maleic anhydride-modified styrene thermoplastic elastomers such as maleic anhydride-modified SEBS. Among these, maleic anhydride-modified EBR and maleic anhydride-modified EOR are preferable.
In addition, the compatibilizing agent in this invention may be used individually by 1 type, and may be used in combination of 2 or more type.

  The weight average molecular weight (in terms of polystyrene) by GPC of the compatibilizing agent is not particularly limited, but is preferably 10,000 to 500,000, more preferably 20,000 to 500,000, still more preferably 30, 000-300,000.

(1-2) Thermoplastic resin composition In the thermoplastic resin composition of the present invention, the content ratio of each component derived from the polyamide resin, polyolefin resin and compatibilizer is not particularly limited.
The content ratio of the component derived from the polyamide resin is preferably 1 to 90% by mass, more preferably 10 to 50% by mass, when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass. %, More preferably 15 to 30% by mass.
The content ratio of the component derived from the polyolefin resin is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass. %, More preferably 40 to 70% by mass.
The content ratio of the component derived from the compatibilizer is preferably 1 to 50% by mass, more preferably 3 to 3% when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass. It is 40 mass%, More preferably, it is 5-30 mass%.

The thermoplastic resin composition of the present invention contains a polyamide resin dispersed in a polyolefin resin. In particular, the smaller the particle size of the dispersed polyamide resin, the better. That is, it is preferable that the polyamide resin is finely dispersed in the polyolefin resin which is a matrix phase.
The average particle size of the dispersed polyamide resin is preferably 10 to 20000 nm, more preferably 50 to 10000 nm, and still more preferably 100 to 5000 nm.
In addition, about the said particle size etc., it can measure based on the image etc. which are obtained using an electron microscope.

The thermoplastic resin composition of the present invention is obtained by melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin.
The “mixed resin” will be described in detail in the method for producing a thermoplastic resin composition described later. Further, the details of the melt-kneading of the mixed resin and the polyolefin resin will be described in the later-described method for producing a thermoplastic resin composition.

[2] Method for producing thermoplastic resin composition The method for producing the thermoplastic resin composition of the present invention is a method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
A mixing step in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin are mixed and kneaded;
The compatibilizing agent is a modified elastomer in which a reactive group capable of reacting with a polyamide resin is added to the elastomer.

(2-1) About each component About the said "polyamide resin", "polyolefin resin", and a "compatibility agent", the above-mentioned description is applicable respectively.

(2-2) Mixing Step The “mixing step” is a step of melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin.
Thus, by using a mixed resin in which a polyamide resin and a compatibilizer are previously melt-kneaded, the compatibilizer can be made to function more effectively. That is, it is considered that the compatibilizer can be prevented from being dispersed alone without functioning in the polyolefin resin by previously mixing the compatibilizer with the polyamide resin to be the dispersed phase. .

The “mixed resin” may be solidified by pelletization or the like, or may be a melt.
For example, the mixed resin may be prepared by kneading a polyamide resin and a compatibilizer with an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader and a mixer (high-speed flow mixer, paddle mixer, ribbon mixer, etc.). It can be obtained by melt-kneading using an apparatus. These apparatuses may use only 1 type and may use 2 or more types together. Moreover, when using 2 or more types, you may drive | operate continuously and may operate | move batchwise (batch type). Further, the polyamide resin and the compatibilizer may be mixed together, or one of them may be added and charged in multiple times (multi-stage blending).
Moreover, the mixing temperature at the time of melt-kneading the polyamide resin and the compatibilizer is not particularly limited, and can be appropriately adjusted depending on the type of each component. In particular, it is preferable to mix each compound in a molten state. Specifically, this mixing temperature can be 190-350 degreeC, Preferably it is 200-330 degreeC, More preferably, it is 205-310 degreeC.

  In the mixing step, the kneading of the mixed resin and the polyolefin resin may be performed by, for example, an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader and a mixer (high-speed fluid mixer, paddle mixer, ribbon mixer, etc.) ) Or the like. These apparatuses may use only 1 type and may use 2 or more types together. Moreover, when using 2 or more types, you may drive | operate continuously and may operate | move batchwise (batch type). Furthermore, the first mixed resin and the polyolefin resin may be mixed together, or one of them may be added and charged (multistage blending) in a plurality of times.

  The mixing temperature in this mixing step is not particularly limited as long as it is a temperature at which melt kneading can be performed, and can be appropriately adjusted depending on the type of each component. In particular, it is preferable that any compound is mixed in a molten state. Specifically, this mixing temperature can be 190-350 degreeC, Preferably it is 200-330 degreeC, More preferably, it is 205-310 degreeC.

  In this mixing step, (1) the mixed resin solidified by pelletization or the like and the polyolefin resin may be melt-kneaded, or (2) upstream using a multi-stage compounding kneader or the like. After melt-kneading the polyamide resin and the compatibilizer on the side, the polyolefin resin is added on the downstream side in the same apparatus, and the melt-kneaded product (mixed resin) of the polyamide resin and the compatibilizer Mixing may be performed.

In the method for producing the thermoplastic resin composition of the present invention, the blending ratio of the polyamide resin, the polyolefin resin and the compatibilizer is not particularly limited.
The blending ratio of the polyamide resin is preferably 1 to 90% by mass, more preferably 10 to 50% by mass, further preferably 100% by mass when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass. Is 15-30 mass%.
The blending ratio of the polyolefin resin is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass. More preferably, it is 40-70 mass%.
Furthermore, the blending ratio of the compatibilizer is preferably 1 to 50 mass%, more preferably 3 to 40 mass% when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100 mass%. %, More preferably 5 to 30% by mass.

  Moreover, in this invention, you may contain other components other than a polyamide resin, polyolefin resin, and a compatibilizing agent in the range which does not inhibit the objective of this invention. Examples of other components include thermoplastic resins other than those described above, flame retardants, flame retardant aids, fillers, colorants, antibacterial agents, and antistatic agents. These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the other thermoplastic resins include polyester resins (polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polybutylene succinate, polyethylene succinate, polylactic acid) and the like.
Examples of the flame retardant include halogen flame retardant (halogenated aromatic compound), phosphorus flame retardant (nitrogen-containing phosphate compound, phosphate ester, etc.), nitrogen flame retardant (guanidine, triazine, melamine, and These derivatives, etc.), inorganic flame retardants (metal hydroxides, etc.), boron flame retardants, silicone flame retardants, sulfur flame retardants, red phosphorus flame retardants and the like.
Examples of the flame retardant aid include various antimony compounds, metal compounds containing zinc, metal compounds containing bismuth, magnesium hydroxide, and clay silicates.
Examples of the filler include glass components (glass fibers, glass beads, glass flakes, etc.), silica, inorganic fibers (glass fibers, alumina fibers, carbon fibers), graphite, silicate compounds (calcium silicate, aluminum silicate, kaolin, Talc, clay, etc.), metal oxides (iron oxide, titanium oxide, zinc oxide, antimony oxide, alumina, etc.), carbonates and sulfates of metals such as calcium, magnesium, zinc, organic fibers (aromatic polyester fibers, aromatic Polyamide fiber, fluororesin fiber, polyimide fiber, vegetable fiber, etc.)
Examples of the colorant include pigments and dyes.

[3] Molded body The thermoplastic resin composition in the present invention may be molded in any way, and the method is not particularly limited. Further, the shape, size, thickness and the like of the obtained molded body are not particularly limited, and the use thereof is not particularly limited. The molded body is used, for example, as an exterior material, an interior material, a structural material, or the like of an automobile, a railway vehicle, a ship, an airplane, or the like. Among these, examples of the automobile supplies include automobile exterior materials, automotive interior materials, automotive structural materials, and engine room components. Specifically, bumper, spoiler, cowling, front grill, garnish, bonnet, trunk lid, fender panel, door panel, roof panel, instrument panel, door trim, quarter trim, roof lining, pillar garnish, deck trim, tonneau board, package Tray, dashboard, console box, kicking plate, switch base, seat back board, seat frame, armrest, sun visor, intake manifold, engine head cover, engine under cover, oil filter housing, automotive electronic components (ECU, TV monitor, etc.) Housing, air filter box and the like. Furthermore, for example, interior materials such as buildings and furniture, exterior materials, and structural materials may be mentioned. That is, a door cover material, a door structure material, a cover material of various furniture (desks, chairs, shelves, bags, etc.), a structural material, and the like. In addition, a package, a container (such as a tray), a protective member, a partition member, and the like can be given. Further, it can also be applied as a housing and a structure of a home appliance (a thin TV, a refrigerator, a washing machine, a vacuum cleaner, a mobile phone, a portable game machine, a notebook personal computer, etc.).

Hereinafter, the present invention will be described specifically by way of examples.
[1] Production of thermoplastic resin composition using PA11 as polyamide resin and production of test piece <Example 1>
(1) Preparation of mixed resin (A) PA11 (nylon 11 resin, manufactured by Arkema Co., Ltd., product name “Rilsan BMN O”, weight average molecular weight 18,000, melting point 190 ° C.) was used as a polyamide resin, and a compatibilizer ( As C), maleic anhydride-modified EPR (manufactured by Mitsui Chemicals, product name “Tafmer MP0620”, MFR (230 ° C.) = 0.3 g / 10 min) is used, and these pellets are blended as shown in Table 1. After dry blending, the mixture is put into a twin-screw melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), kneading temperature 210 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rotations Mixing was performed under the conditions of / min, and the mixed resin extruded using a pelletizer was cut to prepare mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 1 were charged into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), and kneading temperature 210 ° C The thermoplastic resin composition of Example 1 was mixed under the conditions of an extrusion speed of 2.0 kg / hour and a screw rotation speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellets of the thermoplastic resin composition of Example 1 were put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), and set temperature 210 ° C. and mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Example 2>
(C) As a compatibilizing agent, maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, Inc., product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) is used, and the formulation shown in Table 1 is obtained. Thus, the pellet of the thermoplastic resin composition of Example 2 was produced like Example 1 except having dry-blended each pellet. Next, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties in Example 2.

<Example 3>
(C) As a compatibilizer, maleic anhydride-modified SEBS (manufactured by Asahi Kasei Chemicals Corporation, product name “Tuftec M1913”, MFR (230 ° C.) = 5.0 g / 10 min) is used, and the formulation shown in Table 1 is obtained. Thus, the pellet of the thermoplastic resin composition of Example 3 was produced like Example 1 except having dry-blended each pellet. Subsequently, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties in Example 3.

<Example 4>
(C) As a compatibilizing agent, maleic anhydride-modified EOR (manufactured by Dow Chemical Co., Ltd., product name “AMPLIFY GR216”, weight average molecular weight 150,000, maleic anhydride modified amount = 0.8 wt%) was used. A pellet of the thermoplastic resin composition of Example 4 was produced in the same manner as in Example 1 except that each pellet was dry blended so as to have the composition shown in FIG. Next, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties in Example 4.

<Examples 5 to 18>
(C) As a compatibilizing agent, maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tafmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) is used and shown in Tables 1 and 2 Except having dry-blended each pellet so that it might become a mixing | blending, it carried out similarly to Example 1, and produced the pellet of the thermoplastic resin composition of Examples 5-18. Next, injection molding was performed in the same manner as in Example 1 to obtain test pieces for measuring physical properties of Examples 5 to 18.

<Comparative Example 1>
(C) As a compatibilizing agent, maleic anhydride-modified PP (manufactured by Sanyo Kasei Kogyo Co., Ltd., “Yumex 1001”, weight average molecular weight 40,000, acid value 26) is used, so that the composition shown in Table 2 is obtained. A pellet of the thermoplastic resin composition of Comparative Example 1 was produced in the same manner as Example 1 except that each pellet was dry blended. Subsequently, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties of Comparative Example 1.

<Comparative example 2>
(C) As a compatibilizer, unmodified EPR (manufactured by Mitsui Chemicals, Inc., product name “Tafmer P-0680”, MFR (230 ° C.) = 0.7 g / 10 min) is used. A pellet of the thermoplastic resin composition of Comparative Example 2 was produced in the same manner as in Example 1 except that each pellet was dry blended. Subsequently, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties of Comparative Example 2.

<Comparative Example 3>
(C) As a compatibilizer, unmodified EBR (Mitsui Chemicals, product name “Toughmer A-1070S”, MFR (230 ° C.) = 2.2 g / 10 min) is used, A pellet of the thermoplastic resin composition of Comparative Example 3 was produced in the same manner as in Example 1 except that each pellet was dry blended. Subsequently, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties of Comparative Example 3.

<Comparative example 4>
(C) As a compatibilizer, unmodified SEBS (manufactured by Asahi Kasei Chemicals Corporation, product name “Tuftec H1041”, MFR (230 ° C.) = 5 g / 10 min) was used. A pellet of the thermoplastic resin composition of Comparative Example 4 was produced in the same manner as in Example 1 except that the pellets were dry blended. Next, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties of Comparative Example 4.

<Comparative Example 5>
As the polyolefin resin, a polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “NOVATEC MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as a twin-screw melt kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm). , L / D = 59), mixing at a kneading temperature of 210 ° C., an extrusion speed of 2.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded with a pelletizer The composition was cut to produce pellets of the thermoplastic resin composition of Comparative Example 5 (see Table 2). Next, injection molding was performed in the same manner as in Example 1 to obtain a test piece for measuring physical properties of Comparative Example 5.

[2] Performance evaluation of thermoplastic resin compositions (Examples 1 to 18 and Comparative Examples 1 to 5)
(1) Measurement of Charpy impact strength Using the test pieces for measuring physical properties of Examples 1 to 18 and Comparative Examples 1 to 5 obtained in [1] above, Charpy impact strength was measured according to JIS K7111-1. Measurements were made. The results are shown in Table 3, FIG. 1 (Examples 1 to 4 and Comparative Examples 1 to 4) and FIG. 2 (Examples 1 to 4 and Comparative Examples 1 to 4). In this Charpy impact strength measurement, a test piece having a notch (type A) was used, and the impact was measured by an edgewise test method at a temperature of 23 ° C.

(2) Measurement of flexural modulus Using the test pieces for measuring physical properties of Examples 1 to 18 and Comparative Examples 1 to 5 obtained in [1] above, the flexural modulus is measured according to JIS K7171. went. The results are shown in Table 3. This bending elastic modulus is measured at a speed of 2 mm from an action point (curvature radius 5 mm) arranged at the center between the fulcrums while supporting each test piece at two fulcrums (curvature radius 5 mm) with a distance (L) between the fulcrums of 64 mm. The measurement was performed by applying a load at / min.

(3) Morphological observation The fracture surface of the test piece for measuring physical properties of Example 2 subjected to Charpy impact strength measurement in [2] (1) above was magnified 5000 times with a scanning electron microscope (manufactured by JEOL Ltd.). An image obtained by enlarging the image is shown in FIG.

[3] Effects of Examples 1-18 According to Table 3, in Comparative Examples 1-4 using modified polypropylene or unmodified elastomer as a compatibilizer, the flexural modulus was 1251-1386 MPa. The impact strength was a low value of 1.4 to 4.2 kJ / m ² . In Comparative Example 5 in which the polyamide resin and the compatibilizer were not used, the flexural modulus was 1476 MPa, but the Charpy impact strength was a low value of 2.48 kJ / m ² .
On the other hand, in Examples 1-18 using a modified elastomer as a compatibilizing agent, the flexural modulus is 710-1241 MPa, the Charpy impact strength is 6.4-86.3 kJ / m ² , and the rigidity It was found that it was excellent in impact resistance as well as in resistance.

In particular, as is clear from FIG. 1 and Table 3, it was confirmed that the impact resistance could be improved while maintaining sufficient rigidity by modifying the elastomer as the compatibilizer.
Specifically, the Charpy impact strength of Comparative Example 2 using unmodified EPR as a compatibilizer was 2.7 kJ / m ² , whereas that of Example 1 using maleic anhydride-modified EPR was used. The Charpy impact strength was 6.5 kJ / m ² , confirming a significant improvement in impact resistance. The Charpy impact strength of Comparative Example 3 using unmodified EBR was 4.2 kJ / m ² , whereas the Charpy impact strength of Example 2 using maleic anhydride-modified EBR was 10.1 kJ / m ² and a significant improvement in impact resistance was confirmed. Furthermore, the Charpy impact strength of Comparative Example 4 using unmodified SEBS was 2.8 kJ / m ² , whereas the Charpy impact strength of Example 3 using maleic anhydride-modified SEBS was 7 kJ / m ^2. Thus, a significant improvement in impact resistance was confirmed.

Further, as apparent from FIG. 2 and Table 3, it was confirmed that the impact resistance could be improved while maintaining sufficient rigidity by using a modified elastomer among the modified substances as a compatibilizing agent.
Specifically, the Charpy impact strength of Comparative Example 1 using modified polypropylene as a compatibilizer was 1.4 kJ / m ² , whereas the Charpy impact of Examples 1 to 4 using a modified elastomer. The strength was 6.5 to 10.1 kJ / m ² , confirming a significant improvement in impact resistance.

  Moreover, it turns out that the test piece of Example 2 is exhibiting a sea-island structure from the result of FIG. It can be confirmed that most of the island phase (that is, the polyamide resin that is the dispersed phase) is uniformly finely dispersed with an average particle diameter of about 800 nm in the sea phase (that is, the polypropylene resin that is the mother phase). From this, it can be considered that both the impact resistance characteristics and the rigidity characteristics are effectively improved by this structure obtained by using a specific compatibilizer.

[4] Production of thermoplastic resin composition using resin other than PA11 as polyamide resin and production of test piece <Example 19>
(1) Preparation of mixed resin (A) PA6 (nylon 6 resin, Ube Industries, Ltd., product name “1010X1”, melting point 225 ° C.) is used as a polyamide resin, and maleic anhydride modified as a compatibilizer (C) Using EBR (Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min), these pellets were dry blended so as to have the composition shown in Table 4, and then biaxial It is put into a melt kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm, L / D = 59), and mixing is performed under conditions of kneading temperature 260 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rpm. Furthermore, the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 4 were put into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), and kneading temperature 260 ° C. The thermoplastic resin composition of Example 19 was mixed under the conditions of an extrusion speed of 2.0 kg / hour and a screw rotational speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellets of the thermoplastic resin composition of Example 19 were put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), a set temperature of 260 ° C., a mold temperature of 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Examples 20 to 24>
As shown in Table 4, Examples 20 to 20 were carried out in the same manner as in Example 19 except that the following (C) compatibilizers were used and each pellet was dry blended so as to have the formulation shown in Table 4. Twenty-four thermoplastic resin composition pellets were prepared. Subsequently, injection molding was performed in the same manner as in Example 19 to obtain test pieces for measuring physical properties of Examples 20 to 24.
(Details of the compatibilizer (C) used in each example)
Example 20: Maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, Inc., product name “Tafmer MA8510”, MFR (230 ° C.) = 5.0 g / 10 min)
Example 21: Maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, Inc., product name “Tuffmer MH7010”, MFR (230 ° C.) = 1.8 g / 10 min)
Example 22: Maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tafmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min)
Example 23: Maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tafmer MH5040”, MFR (230 ° C.) = 1.1 g / 10 min)
Example 24: Maleic anhydride modified EOR (manufactured by Dow Chemical Co., Ltd., product name “AMPLIFY GR216”, weight average molecular weight 150,000, maleic anhydride modified amount = 0.8 wt%)

<Comparative Example 6>
(A) PA6 (nylon 6 resin, manufactured by Ube Industries, product name “1010X1”, melting point 225 ° C.) as the polyamide resin, and (B) polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “ Novatec MA1B ”, weight average molecular weight 312,000, melting point 165 ° C., and after dry blending so as to have the composition shown in Table 4, twin-screw melt kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59), mixing at a kneading temperature of 260 ° C., an extrusion speed of 2.0 kg / hour, a screw rotation speed of 200 revolutions / minute, and further extruding the thermoplastic resin composition extruded using a pelletizer The pellet of the thermoplastic resin composition of the comparative example 6 was produced by cutting.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 6 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), and set temperature 260 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Example 25>
(1) Preparation of mixed resin (A) PA12 (nylon 12 resin, manufactured by Arkema Co., Ltd., product name “Rilsan AECN OTL”, melting point 174 to 178 ° C.) was used as a polyamide resin, and anhydrous as a compatibilizer (C) After dry blending these pellets using the maleic acid-modified EBR (Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) so as to have the composition shown in Table 5. And put into a twin-screw melt kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59), under conditions of kneading temperature 210 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rpm. Mixing was performed, and the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 5 were put into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), and kneading temperature 210 ° C The thermoplastic resin composition of Example 25 was mixed under the conditions of an extrusion speed of 2.0 kg / hour and a screw rotational speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellets of the thermoplastic resin composition of Example 25 were put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), a set temperature of 210 ° C., a mold temperature of 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Example 26>
A pellet of the thermoplastic resin composition of Example 26 was produced in the same manner as in Example 25 except that each pellet was dry blended so as to have the composition shown in Table 5. Next, injection molding was performed in the same manner as in Example 25 to obtain a test piece for measuring physical properties of Example 26.

<Comparative Example 7>
As a polyamide resin, PA12 (nylon 12 resin, manufactured by Arkema Co., Ltd., product name “Rilsan AECN OTL”, melting point: 174 to 178 ° C.) was mixed with a twin-screw melt kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59), mixing at a kneading temperature of 210 ° C., an extrusion speed of 2.0 kg / hour, and a screw speed of 200 revolutions / minute, and further cutting the extruded thermoplastic resin composition using a pelletizer. Thus, pellets of the thermoplastic resin composition of Comparative Example 7 were produced (see Table 5). Next, injection molding was performed in the same manner as in Example 25 to obtain a test piece for measuring physical properties of Comparative Example 7.

<Example 27>
(1) Preparation of mixed resin (A) PA 610 (nylon 610 resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid Terra HS16”, melting point 222 ° C.) is used as a compatibilizing agent (C) and anhydrous. After dry blending these pellets using the maleic acid-modified EBR (Mitsui Chemicals Co., Ltd., product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) so as to have the composition shown in Table 6. , Put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 235 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 rpm Then, the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 6 were put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 235 The thermoplastic resin composition of Example 27 was mixed under the conditions of ° C., extrusion speed of 3.0 kg / hour, screw rotation speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellets of the thermoplastic resin composition of Example 27 were put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 235 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Examples 28 to 32>
Except having dry-blended each pellet so that it might become the mixing | blending shown in Table 6, it carried out similarly to Example 27, and produced the pellet of the thermoplastic resin composition of Examples 28-32. Subsequently, injection molding was performed in the same manner as in Example 27, and test pieces for measuring physical properties of Examples 28 to 32 were obtained.

<Comparative Example 8>
(A) PA610 as a polyamide resin (nylon 610 resin, manufactured by Daicel Evonik Co., Ltd., product name “Vestamid Terra HS16”, melting point 222 ° C.) and (B) a polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd.) , Product name “Novatech MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 6, followed by a biaxial melt kneading extruder (manufactured by Parker Corporation, screw) Thermoplastic extruded into a 25 mm diameter, L / D = 41), mixed at a kneading temperature of 235 ° C., an extrusion speed of 3.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded using a pelletizer The pellet of the thermoplastic resin composition of Comparative Example 8 was cut by cutting the resin composition. To prepare a door.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 8 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 235 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Example 33>
(1) Preparation of mixed resin (A) PA1010 (nylon 1010 resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid Terra DS16”, melting point 206 ° C.) is used as a compatibilizing agent (C) and anhydrous. After dry blending these pellets using the maleic acid-modified EBR (Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) so as to have the composition shown in Table 7. , Put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 250 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 rpm In addition, the mixed resin extruded using a pelletizer is cut to produce mixed resin pellets. It was.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. After dry blending with the mixed resin pellets and the composition shown in Table 7, the mixture was put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 250 The thermoplastic resin composition of Example 33 was mixed under the conditions of ° C., extrusion rate of 3.0 kg / hour, screw rotation speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellet of the thermoplastic resin composition of Example 33 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 250 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Examples 34 to 38>
Except having dry-blended each pellet so that it might become the mixing | blending shown in Table 7, it carried out similarly to Example 33, and produced the pellet of the thermoplastic resin composition of Examples 34-38. Subsequently, injection molding was performed in the same manner as in Example 33 to obtain test pieces for measuring physical properties in Examples 34 to 38.

<Comparative Example 9>
(A) PA1010 (nylon 1010 resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid Terra DS16”, melting point 206 ° C.) as the polyamide resin, and (B) polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd.) as the polyolefin resin , Product name “NOVATEC MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 7, followed by a twin-screw melt-kneading extruder (manufactured by Parker Corporation, screw) Thermoplastic extruded into a 25 mm diameter, L / D = 41), mixed at a kneading temperature of 250 ° C., an extrusion speed of 3.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded using a pelletizer The thermoplastic resin composition of Comparative Example 9 was cut by cutting the resin composition. To prepare a toilet.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 9 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), and set temperature 250 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Example 39>
(1) Preparation of mixed resin (A) PAMXD6 (nylon MXD6 resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name “Reny 6002”, melting point 243 ° C.) was used as a polyamide resin, and anhydrous as a compatibilizer (C) After using a maleic acid-modified EBR (Mitsui Chemicals Co., Ltd., product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) and dry-blending these pellets to the formulation shown in Table 8 , Put into a twin-screw melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 265 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 rpm Then, the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 8 were put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 265 The thermoplastic resin composition of Example 39 was mixed under the conditions of ° C., extrusion rate of 3.0 kg / hour, screw rotation speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellet of the thermoplastic resin composition of Example 39 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40-ton injection molding machine), and a set temperature of 265 ° C. and a mold temperature of 90 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Examples 40 to 44>
Except having dry-blended each pellet so that it might become the mixing | blending shown in Table 8, it carried out similarly to Example 39, and produced the pellet of the thermoplastic resin composition of Examples 40-44. Subsequently, injection molding was performed in the same manner as in Example 39 to obtain test pieces for measuring physical properties of Examples 40 to 44.

<Comparative Example 10>
(A) PAMXD6 (nylon MXD6 resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name “Lenny 6002”, melting point 243 ° C.) as the polyamide resin, and (B) polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd.) , Product name “Novatech MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 8, followed by a twin-screw melt kneading extruder (manufactured by Parker Corporation, screw) Thermoplastic extruded into a 25 mm diameter, L / D = 41), mixed at a kneading temperature of 265 ° C., an extrusion speed of 3.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded using a pelletizer The resin composition was cut and the thermoplastic resin composition of Comparative Example 10 was cut. The Tsu door was fabricated.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 10 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40-ton injection molding machine), and a set temperature of 265 ° C. and a mold temperature of 90 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Example 45>
(1) Preparation of mixed resin (A) PA10T (nylon 10T resin, manufactured by Daicel Evonik Co., Ltd., product name “Vestamid HT Plus M3000”, melting point 285 ° C.) was used as a polyamide resin, and as a compatibilizer (C), Using maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min), these pellets were dry blended so as to have the composition shown in Table 9. Thereafter, it is put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 310 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 revolutions / minute. Mixing is performed under the conditions, and the mixed resin extruded using a pelletizer is cut to produce mixed resin pellets. It was.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. After dry blending with the mixed resin pellets as shown in Table 9, the mixture was put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 310 The thermoplastic resin composition of Example 45 was mixed under the conditions of ° C., extrusion rate of 3.0 kg / hour, screw rotation speed of 200 revolutions / minute, and further cut out the extruded thermoplastic resin composition using a pelletizer. A pellet was prepared.
Thereafter, the obtained pellets of the thermoplastic resin composition of Example 45 were put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 310 ° C., mold temperature 90 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Examples 46 to 47>
Except having dry-blended each pellet so that it might become the mixing | blending shown in Table 9, it carried out similarly to Example 45, and produced the pellet of the thermoplastic resin composition of Examples 46-47. Subsequently, injection molding was performed in the same manner as in Example 45 to obtain test pieces for measuring physical properties of Examples 46 to 47.

<Comparative Example 11>
(A) PA10T (Nylon 10T resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid HT Plus M3000”, melting point 285 ° C.) as the polyamide resin, and (B) Polypropylene resin (Homopolymer, Nippon Polypro Co., Ltd.) as the polyolefin resin Manufactured, product name “Novatech MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 9, followed by a biaxial melt kneading extruder (manufactured by Parker Corporation, The screw diameter was 25 mm, L / D = 41), mixing was performed at a kneading temperature of 310 ° C., an extrusion speed of 3.0 kg / hour, a screw rotation speed of 200 revolutions / minute, and the heat extruded using a pelletizer The thermoplastic resin composition of Comparative Example 11 by cutting the plastic resin composition A pellet was prepared.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 11 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 310 ° C., mold temperature 90 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

[5] Performance evaluation of thermoplastic resin compositions (Examples 19 to 47 and Comparative Examples 6 to 11)
Using the specimens for measuring physical properties of Examples 19 to 47 and Comparative Examples 6 to 11 obtained in [4] above, measurement of Charpy impact strength and bending elastic modulus were performed in the same manner as in [2] above. Was measured. The results are also shown in Tables 4-9.

[6] Effects of Examples 19 to 47 According to Table 4, in Comparative Example 6 in which PA6 was used as the polyamide and no compatibilizer was used, the flexural modulus was 2022 MPa, but the Charpy impact strength was The value was as low as 2.3 kJ / m ² .
On the other hand, in Examples 19 to 24 using PA6 as the polyamide and the modified elastomer as the compatibilizer, the flexural modulus is 1325 to 1467 MPa, and the Charpy impact strength is 3.9 to 16.6 kJ / m ² , which was found to be excellent in rigidity and impact resistance.

According to Table 5, in Comparative Example 7 where only PA12 was used as the polyamide and no polyolefin and no compatibilizer were used, the flexural modulus was 1340 MPa, but the Charpy impact strength was 2.8 kJ / m ² . It was a low value.
On the other hand, in Examples 25 to 26 using PA12 as the polyamide and using the modified elastomer as the compatibilizer, the flexural modulus is 1253 to 1434 MPa, and the Charpy impact strength is 7.7 to 12.8 kJ /. m ² , which was found to be excellent in rigidity and impact resistance.

According to Table 6, in Comparative Example 8 in which PA610 was used as the polyamide and no compatibilizer was used, the flexural modulus was 1730 MPa, but the Charpy impact strength was as low as 2.1 kJ / m ^2. there were.
On the other hand, in Examples 27 to 32 using PA610 as the polyamide and the modified elastomer as the compatibilizer, the flexural modulus is 660 to 1390 MPa, and the Charpy impact strength is 5.4 to 40.0 kJ / m ² , which was found to be excellent in rigidity and impact resistance.

According to Table 7, in Comparative Example 9 in which PA1010 was used as the polyamide and no compatibilizer was used, the flexural modulus was 1650 MPa, but the Charpy impact strength was as low as 1.1 kJ / m ^2. there were.
In contrast, in Examples 33 to 38 using PA1010 as the polyamide and the modified elastomer as the compatibilizing agent, the flexural modulus was 550 to 1350 MPa, and the Charpy impact strength was 2.1 to 40.0 kJ / m ² , which was found to be excellent in rigidity and impact resistance.

According to Table 8, in Comparative Example 10 where PAMXD6 was used as the polyamide and no compatibilizer was used, the flexural modulus was 2270 MPa, but the Charpy impact strength was a low value of 1.1 kJ / m ^2. there were.
On the other hand, in Examples 39 to 44 using PAMXD6 as the polyamide and the modified elastomer as the compatibilizer, the flexural modulus is 820 to 2640 MPa, and the Charpy impact strength is 2.2 to 56.0 kJ / m ² , which was found to be excellent in rigidity and impact resistance.

According to Table 9, in Comparative Example 11 in which PA10T was used as the polyamide and no compatibilizer was used, the flexural modulus was 1860 MPa, but the Charpy impact strength was as low as 1.1 kJ / m ^2. there were.
On the other hand, in Examples 45 to 47 using PA10T as the polyamide and using the modified elastomer as the compatibilizer, the flexural modulus is 910 to 1620 MPa, and the Charpy impact strength is 2.1 to 5.0 kJ / m ² , which was found to be excellent in rigidity and impact resistance.

  The foregoing examples are for illustrative purposes only and are not to be construed as limiting the invention. Although the invention has been described with reference to exemplary embodiments, it is to be understood that the language used in the description and illustration of the invention is illustrative and exemplary rather than limiting. As detailed herein, changes may be made in its form within the scope of the appended claims without departing from the scope or spirit of the invention. Although specific structures, materials and examples have been referred to in the detailed description of the invention herein, it is not intended to limit the invention to the disclosures presented herein, but rather, the invention is claimed. It covers all functionally equivalent structures, methods and uses within the scope of

The present invention relates to a thermoplastic resin composition. More particularly, the present invention has excellent rigidity, relates to a thermoplastic resin composition excellent in impact resistance.

2. Description of the Related Art Conventionally, polymer blends (including polymer alloys) in which resins having different polarities are mixed to modify the properties of the resin have been actively studied (see, for example, Patent Documents 1 and 2).
At that time, if the compatibility between the resins is insufficient, the mechanical properties such as impact resistance properties are reduced, and the modification effect by the polymer blend may not be obtained. It is necessary to improve compatibility. For example, in the case of a polymer alloy of a polypropylene resin and a polyamide resin, a method of using a compatibilizing agent such as maleic anhydride-modified polypropylene has been proposed in order to improve the compatibility.

JP 2007-297441 A JP 2009-203410 A

In the fields of automobile interior parts and exterior parts, high mechanical properties are required, and it is indispensable to satisfy both impact resistance and rigidity (flexural modulus).
However, in the above-mentioned polymer blend, the impact resistance characteristics and the rigidity characteristics are in a trade-off relationship with each other, and in particular, there is a conflicting relationship that the rigidity is insufficient by utilizing the impact resistance characteristics. However, the present situation has yet to be obtained that sufficiently satisfy the characteristics of both.

This invention is made | formed in view of the said situation, and it aims at providing the thermoplastic resin composition which is excellent also in an impact-resistant characteristic while being excellent in rigidity.

In order to solve the above-mentioned problems, the invention described in claim 1 includes a polyamide resin (excluding clay mineral-modified polyamide) and a compatibilizing agent, and a polyolefin resin (excluding modified polypropylene). A thermoplastic resin composition containing a melt-kneaded product with
In the polyolefin resin, the polyamide resin is dispersed and contained,
The compatibilizer agents, Ri modified elastomer der reactive group is applied capable of reacting with the polyamide resin to the elastomer,
The elastomer is an ethylene-propylene copolymer (EPR),
When the total of the polyolefin resin, the polyamide resin, and the compatibilizer is 100% by mass,
The content of the component derived from the polyolefin resin is 20 to 70% by mass,
The content of the component derived from the polyamide resin is 10 to 50% by mass,
The gist of the content of the component derived from the compatibilizer is 10 to 50% by mass .
The invention according to claim 2 is the invention according to claim 1, wherein the total of the polyolefin resin, the polyamide resin, and the compatibilizer is 100% by mass.
The content of the component derived from the polyolefin resin is 40 to 70% by mass,
The content of the component derived from the polyamide resin is 15 to 40% by mass,
The content of the component derived from the compatibilizing agent is 15 to 40% by mass .

According to the thermoplastic resin composition of the present invention, since it is obtained by melt-kneading a mixed resin in which a polyamide resin and a specific compatibilizer are melt-kneaded and a polyolefin resin, it has excellent rigidity. Excellent impact resistance.
Moreover, elastomer, because it is specific olefinic thermoplastic elastomer, better impact resistance and rigidity is obtained.

It is a graph regarding Charpy impact strength. It is a graph regarding Charpy impact strength. It is explanatory drawing explaining the dispersion state of resin by SEM observation.

  The items shown here are for illustrative purposes and exemplary embodiments of the present invention, and are the most effective and easy-to-understand explanations of the principles and conceptual features of the present invention. It is stated for the purpose of providing what seems to be. In this respect, it is not intended to illustrate the structural details of the present invention beyond what is necessary for a fundamental understanding of the present invention. It will be clear to those skilled in the art how it is actually implemented.

[1] Thermoplastic resin composition The thermoplastic resin composition of the present invention is a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
Obtained by melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin,
The compatibilizing agent is a modified elastomer in which a reactive group capable of reacting with a polyamide resin is added to the elastomer.

(1-1) About Each Component The “polyamide resin” is a polymer having a chain skeleton formed by polymerizing a plurality of monomers via an amide bond (—NH—CO—). The thermoplastic resin composition according to the present invention is a resin that forms a dispersed phase with respect to a polyolefin resin described later.

  Examples of the monomer constituting the polyamide resin include aminocaproic acid, aminoundecanoic acid, aminododecanoic acid, amino acids such as paraaminomethylbenzoic acid, and lactams such as ε-caprolactam, undecane lactam, and ω-lauryllactam. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Furthermore, the polyamide resin can also be obtained by copolymerization of a diamine and a dicarboxylic acid. In this case, the diamine as a monomer is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, , 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1, 16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, 2-methyl Aliphatic diamine such as -1,8-diaminooctane, cyclohexanediamine, bi - (4-aminocyclohexyl) cycloaliphatic diamines such as methane, aromatic diamines such as xylylenediamine (p- phenylenediamine and m- phenylenediamine and the like). These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Furthermore, as the dicarboxylic acid as a monomer, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, Aliphatic dicarboxylic acids such as tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid Etc. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, the polyamide resin is preferably a polyamide resin containing an amide bond-containing unit having 11 carbon atoms in the main chain. That is, a polyamide resin containing a structural unit derived from a monomer having 11 carbon atoms is preferable, and a polymer using 11-aminoundecanoic acid or undecane lactam as a monomer (hereinafter referred to as this heavy polymer). The coalescence is also referred to as “PA11 resin”. In particular, 11-aminoundecanoic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutral).
It is preferable that the structural unit derived from the monomer having 11 carbon atoms is 50% or more of all the structural units in the PA11 resin. That is, a structural unit derived from a monomer having a carbon atom number of less than 11 and / or a structural unit derived from a monomer having a carbon atom number of 12 or more are all structural units in the PA11 resin. It can contain less than 50% of them. Further, the PA11-based resin may be a structural unit derived from a monomer having all the structural units of 11 carbon atoms. That is, the polyamide resin may be polyamide 11 (PA11).

In the present invention, examples of preferable polyamide (A) other than the PA11 resin include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, and polyamide. M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T, polyamide 9T / 2M-8T, and the like.
In addition, these polyamide (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

Moreover, when using together PA11 type | system | group resin and another polyamide, when the whole polyamide resin is 100 mass%, the content rate of another polyamide can be made into less than 40 mass%.
In the polyamide resin, it is preferable that half or more (50% or more) of carbon atoms constituting the main chain constitute a chain skeleton. That is, the polyamide resin may contain an aromatic skeleton, but the number of carbon atoms constituting the aromatic skeleton is preferably less than half (less than 50%) of the carbon atoms constituting the main chain.

  Although the weight average molecular weight (polystyrene conversion) by the gel permeation chromatography (GPC) of a polyamide resin is not specifically limited, It is preferable that it is 5,000-100,000, More preferably, it is 7,500-50,000, Furthermore, Preferably it is 10,000-50,000.

The “polyolefin resin” is a resin that forms a continuous phase with respect to the polyamide resin in the thermoplastic resin composition according to the present invention.
The polyolefin resin is not particularly limited, and various polyolefins can be used. Examples thereof include an ethylene homopolymer, a propylene homopolymer, an ethylene-propylene copolymer, an ethylene-α-olefin copolymer, and a propylene-α-olefin copolymer.
The α-olefin is usually an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and includes propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 3-methyl-1-butene, 4-methyl-1-pentene and the like can be mentioned.
These polyolefin resins may be used individually by 1 type, and may be used in combination of 2 or more type. That is, the polyolefin resin may be a mixture of the above polymers.

  Although the weight average molecular weight (polystyrene conversion) of polyolefin resin by GPC is not specifically limited, It is preferable that it is 10,000-500,000, More preferably, it is 100,000-450,000, More preferably, it is 200,000- 400,000.

Incidentally, the polyolefin resin is a polyolefin having no affinity for the polyamide resin, and, Ru polyolefin der without also reactive group capable of reacting the polyamide resin.

The “compatibility agent” is a modified elastomer in which a reactive group capable of reacting with a polyamide resin is added to the elastomer.
As the elastomer, OH olefin-based thermoplastic elastomers, may be mentioned styrene-based thermoplastic elastomer, in the present invention, olefin-based thermoplastic elastomer is used.

The o olefin-based thermoplastic elastomers, ethylene, propylene, 1-butene, 1-pentene, alpha-olefins such as 1-octene those obtained by copolymerizing, in particular, et styrene and 3 to 8 carbon atoms in the alpha- polymer of an olefin, and a polymer of propylene and 4 to 8 carbon atoms α- olefin.
Specific examples of the olefin-based thermoplastic elastomer include ethylene-propylene copolymer (EPR), ethylene-1-butene copolymer (EBR), ethylene-1-pentene copolymer, and ethylene-1-octene copolymer. polymer (EOR), propylene-1-butene copolymer (PBR), a propylene-1-pentene copolymer, propylene, 1-octene copolymer (POR), and the like, in the present invention, ethylene -Propylene copolymer (EPR) is used.

The scan styrene-based thermoplastic elastomer, a block copolymer of styrene compound and conjugated diene compound, and its hydrogenated derivative thereof.
Examples of the styrene compound include alkyl styrene such as styrene, α-methyl styrene, p-methyl styrene, and pt-butyl styrene, p-methoxy styrene, and vinyl naphthalene.
Examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and the like.

Specific examples of the styrene thermoplastic elastomer include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and styrene-ethylene / butylene-styrene copolymer (SEBS). And styrene-ethylene / propylene-styrene copolymer (SEPS) .

The reactive group capable of reacting with the polyamide resin includes an acid anhydride group (—CO—O—OC—), a carboxyl group (—COOH), an epoxy group [—C ₂ O (two carbon atoms and 1 A three-membered ring structure composed of two oxygen atoms)], an oxazoline group (—C ₃ H ₄ NO), an isocyanate group (—NCO), and the like. In addition, the method for imparting these reactive groups to the elastomer is not particularly limited, and a known method can be used.

Among the reactive groups described above, an acid anhydride group is particularly preferable. Examples of the monomer for introducing the acid anhydride group include maleic anhydride, phthalic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. And acid anhydrides such as butenyl succinic anhydride. Among these, maleic anhydride, phthalic anhydride, and itaconic anhydride are preferable, and maleic anhydride is particularly preferable.
In addition, these monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, when using the modified elastomer into which acid groups, such as an acid anhydride group, were used as a compatibilizing agent, the amount of acid groups is not particularly limited.

Here, as a specific modified elastomer used as the compatibilizer of the present invention, for example, maleic anhydride-modified EPR and the like can be mentioned .
In addition, the compatibilizing agent in this invention may be used individually by 1 type, and may be used in combination of 2 or more type.

  The weight average molecular weight (in terms of polystyrene) by GPC of the compatibilizing agent is not particularly limited, but is preferably 10,000 to 500,000, more preferably 20,000 to 500,000, still more preferably 30, 000-300,000.

(1-2) In the thermoplastic resin composition of the present invention for the thermoplastic resin composition, the content of components derived from polyamides resin, a polyamide resin, the sum of the polyolefin resin and compatibilizer 100 wt% In this case, it is 10 to 50% by mass, more preferably 15 to 30% by mass.
The content ratio of the component derived from the polyolefin resin is 20 to 70% by mass when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass.
The content ratio of the component derived from the compatibilizer is preferably 10 to 50% by mass, more preferably 10 to 10 % when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass. 40 wt%, more preferably 10 weight to 30% by weight.

The thermoplastic resin composition of the present invention contains a polyamide resin dispersed in a polyolefin resin. In particular, the smaller the particle size of the dispersed polyamide resin, the better. That is, it is preferable that the polyamide resin is finely dispersed in the polyolefin resin which is a matrix phase.
The average particle size of the dispersed polyamide resin is preferably 10 to 20000 nm, more preferably 50 to 10000 nm, and still more preferably 100 to 5000 nm.
In addition, about the said particle size etc., it can measure based on the image etc. which are obtained using an electron microscope.

The thermoplastic resin composition of the present invention is obtained by melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin.
The “mixed resin” will be described in detail in the method for producing a thermoplastic resin composition described later. Further, the details of the melt-kneading of the mixed resin and the polyolefin resin will be described in the later-described method for producing a thermoplastic resin composition.

[2] Method for Producing Thermoplastic Resin Composition The thermoplastic resin composition of the present invention comprises a mixing step in which a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin are melt-kneaded. It can be manufactured by a method .

(2-1) About each component About the said "polyamide resin", "polyolefin resin", and a "compatibility agent", the above-mentioned description is applicable respectively.

(2-2) Mixing Step The “mixing step” is a step of melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin.
Thus, by using a mixed resin in which a polyamide resin and a compatibilizer are previously melt-kneaded, the compatibilizer can be made to function more effectively. That is, it is considered that the compatibilizer can be prevented from being dispersed alone without functioning in the polyolefin resin by previously mixing the compatibilizer with the polyamide resin to be the dispersed phase. .

The “mixed resin” may be solidified by pelletization or the like, or may be a melt.
For example, the mixed resin may be prepared by kneading a polyamide resin and a compatibilizer with an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader and a mixer (high-speed flow mixer, paddle mixer, ribbon mixer, etc.). It can be obtained by melt-kneading using an apparatus. These apparatuses may use only 1 type and may use 2 or more types together. Moreover, when using 2 or more types, you may drive | operate continuously and may operate | move batchwise (batch type). Further, the polyamide resin and the compatibilizer may be mixed together, or one of them may be added and charged in multiple times (multi-stage blending).
Moreover, the mixing temperature at the time of melt-kneading the polyamide resin and the compatibilizer is not particularly limited, and can be appropriately adjusted depending on the type of each component. In particular, it is preferable to mix each compound in a molten state. Specifically, this mixing temperature can be 190-350 degreeC, Preferably it is 200-330 degreeC, More preferably, it is 205-310 degreeC.

  In the mixing step, the kneading of the mixed resin and the polyolefin resin may be performed by, for example, an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader and a mixer (high-speed fluid mixer, paddle mixer, ribbon mixer, etc.) ) Or the like. These apparatuses may use only 1 type and may use 2 or more types together. Moreover, when using 2 or more types, you may drive | operate continuously and may operate | move batchwise (batch type). Furthermore, the first mixed resin and the polyolefin resin may be mixed together, or one of them may be added and charged (multistage blending) in a plurality of times.

  The mixing temperature in this mixing step is not particularly limited as long as it is a temperature at which melt kneading can be performed, and can be appropriately adjusted depending on the type of each component. In particular, it is preferable that any compound is mixed in a molten state. Specifically, this mixing temperature can be 190-350 degreeC, Preferably it is 200-330 degreeC, More preferably, it is 205-310 degreeC.

  In this mixing step, (1) the mixed resin solidified by pelletization or the like and the polyolefin resin may be melt-kneaded, or (2) upstream using a multi-stage compounding kneader or the like. After melt-kneading the polyamide resin and the compatibilizer on the side, the polyolefin resin is added on the downstream side in the same apparatus, and the melt-kneaded product (mixed resin) of the polyamide resin and the compatibilizer Mixing may be performed.

In the manufacturing method of the thermoplastic resin composition of the present invention, the mixing ratio of the polyamides resin, when the polyamide resin, the total of the polyolefin resin and the compatibilizer is 100 mass%, 1 0-50% by weight, further Preferably it is 15-30 mass%.
The blending ratio of the polyolefin resin is 20 to 70% by mass when the total of the polyamide resin, the polyolefin resin and the compatibilizer is 100% by mass.
Furthermore, the blending ratio of the compatibilizer is preferably 10 to 50% by mass, more preferably 10 to 40% by mass when the total of the polyamide resin, polyolefin resin and compatibilizer is 100% by mass. %, More preferably 10 to 30% by mass.

  Moreover, in this invention, you may contain other components other than a polyamide resin, polyolefin resin, and a compatibilizing agent in the range which does not inhibit the objective of this invention. Examples of other components include thermoplastic resins other than those described above, flame retardants, flame retardant aids, fillers, colorants, antibacterial agents, and antistatic agents. These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the other thermoplastic resins include polyester resins (polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polybutylene succinate, polyethylene succinate, polylactic acid) and the like.
Examples of the flame retardant include halogen flame retardant (halogenated aromatic compound), phosphorus flame retardant (nitrogen-containing phosphate compound, phosphate ester, etc.), nitrogen flame retardant (guanidine, triazine, melamine, and These derivatives, etc.), inorganic flame retardants (metal hydroxides, etc.), boron flame retardants, silicone flame retardants, sulfur flame retardants, red phosphorus flame retardants and the like.
Examples of the flame retardant aid include various antimony compounds, metal compounds containing zinc, metal compounds containing bismuth, magnesium hydroxide, and clay silicates.
Examples of the filler include glass components (glass fibers, glass beads, glass flakes, etc.), silica, inorganic fibers (glass fibers, alumina fibers, carbon fibers), graphite, silicate compounds (calcium silicate, aluminum silicate, kaolin, Talc, clay, etc.), metal oxides (iron oxide, titanium oxide, zinc oxide, antimony oxide, alumina, etc.), carbonates and sulfates of metals such as calcium, magnesium, zinc, organic fibers (aromatic polyester fibers, aromatic Polyamide fiber, fluororesin fiber, polyimide fiber, vegetable fiber, etc.)
Examples of the colorant include pigments and dyes.

[3] Molded body The thermoplastic resin composition in the present invention may be molded in any way, and the method is not particularly limited. Further, the shape, size, thickness and the like of the obtained molded body are not particularly limited, and the use thereof is not particularly limited. The molded body is used, for example, as an exterior material, an interior material, a structural material, or the like of an automobile, a railway vehicle, a ship, an airplane, or the like. Among these, examples of the automobile supplies include automobile exterior materials, automotive interior materials, automotive structural materials, and engine room components. Specifically, bumper, spoiler, cowling, front grill, garnish, bonnet, trunk lid, fender panel, door panel, roof panel, instrument panel, door trim, quarter trim, roof lining, pillar garnish, deck trim, tonneau board, package Tray, dashboard, console box, kicking plate, switch base, seat back board, seat frame, armrest, sun visor, intake manifold, engine head cover, engine under cover, oil filter housing, automotive electronic components (ECU, TV monitor, etc.) Housing, air filter box and the like. Furthermore, for example, interior materials such as buildings and furniture, exterior materials, and structural materials may be mentioned. That is, a door cover material, a door structure material, a cover material of various furniture (desks, chairs, shelves, bags, etc.), a structural material, and the like. In addition, a package, a container (such as a tray), a protective member, a partition member, and the like can be given. Further, it can also be applied as a housing and a structure of a home appliance (a thin TV, a refrigerator, a washing machine, a vacuum cleaner, a mobile phone, a portable game machine, a notebook personal computer, etc.).

Hereinafter, the present invention will be described specifically by way of examples.
[1] Manufacture of a thermoplastic resin composition using PA11 as a polyamide resin and preparation of a test piece (Note that, of the following Experimental Examples 1 to 18, Experimental Example 1 is an Example, and Experimental Examples 2 to 18 are for reference. An example.)
<Experimental Example 1>
(1) Preparation of mixed resin (A) PA11 (nylon 11 resin, manufactured by Arkema Co., Ltd., product name “Rilsan BMN O”, weight average molecular weight 18,000, melting point 190 ° C.) was used as a polyamide resin, and a compatibilizer ( As C), maleic anhydride-modified EPR (manufactured by Mitsui Chemicals, product name “Tafmer MP0620”, MFR (230 ° C.) = 0.3 g / 10 min) is used, and these pellets are blended as shown in Table 1. After dry blending, the mixture is put into a twin-screw melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), kneading temperature 210 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rotations Mixing was performed under the conditions of / min, and the mixed resin extruded using a pelletizer was cut to prepare mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 1 were charged into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), and kneading temperature 210 ° C. , extrusion rate 2.0 kg / time, and mixed and the conditions of a screw speed of 200 revolutions / minute, further, the thermoplastic resin composition of experiment example 1 was cut to a thermoplastic resin composition extruded by using a pelletizer Article pellets were made.
Then, the pellets of the obtained thermoplastic resin composition of Experiment Example 1, an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of a preset temperature of 210 ° C., mold temperature A test piece for measuring physical properties was injection molded under injection conditions of 60 ° C.

<Experimental Example 2>
(C) As a compatibilizing agent, maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) is used, and the formulation shown in Table 1 is obtained. except that each pellet was dry-blended as was to prepare pellets of experiment example 1 and the thermoplastic resin composition of experiment example 2 in the same manner. Next, by injection molding in the same manner as Experiment Example 1, to obtain a measurement of physical properties for test specimens of experiments Example 2.

<Experimental Example 3>
(C) As a compatibilizer, maleic anhydride-modified SEBS (manufactured by Asahi Kasei Chemicals Corporation, product name “Tuftec M1913”, MFR (230 ° C.) = 5.0 g / 10 min) is used, and the formulation shown in Table 1 is obtained. except that each pellet was dry-blended as is, to prepare a pellet of the thermoplastic resin composition of the experimental example 3 in the same manner as experiment example 1. Next, by injection molding in the same manner as Experiment Example 1, to obtain a measurement of physical properties for test specimens of experiments Example 3.

<Experimental Example 4>
(C) As a compatibilizing agent, maleic anhydride-modified EOR (manufactured by Dow Chemical Co., Ltd., product name “AMPLIFY GR216”, weight average molecular weight 150,000, maleic anhydride modified amount = 0.8 wt%) was used. except that dry blending each pellet so that the composition shown in the pellets were produced in the thermoplastic resin composition of experimental example 1 experimental example in the same manner as in 4. Next, by injection molding in the same manner as Experiment Example 1, to obtain a measurement of physical properties for test specimens of experiments Example 4.

<Experimental Example 5 to 18>
(C) As a compatibilizing agent, maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tafmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) is used and shown in Tables 1 and 2 except that dry blending each pellet so that the formulation was to prepare pellets of the thermoplastic resin composition of the experimental example 5 to 18 in the same manner as in experiment example 1. Next, by injection molding in the same manner as Experiment Example 1, to obtain a measurement of physical properties for test specimens of experiments Examples 5-18.

<Comparative Example 1>
(C) As a compatibilizing agent, maleic anhydride-modified PP (manufactured by Sanyo Kasei Kogyo Co., Ltd., “Yumex 1001”, weight average molecular weight 40,000, acid value 26) is used, so that the composition shown in Table 2 is obtained. except that each pellet was dry blends were prepared pellets of the thermoplastic resin composition of Comparative example 1 in the same manner as in experiment example 1. Next, by injection molding in the same manner as Experiment Example 1, to obtain a physical property measurement for the test piece of Comparative Example 1.

<Comparative example 2>
(C) As a compatibilizer, unmodified EPR (manufactured by Mitsui Chemicals, Inc., product name “Tafmer P-0680”, MFR (230 ° C.) = 0.7 g / 10 min) is used. except that each pellet was dry-blended so as to prepare a pellet of the to the thermoplastic resin composition of Comparative example 2 similarly to experimental example 1. Next, by injection molding in the same manner as Experiment Example 1, to obtain a physical property measurement for the test piece of Comparative Example 2.

<Comparative Example 3>
(C) As a compatibilizer, unmodified EBR (Mitsui Chemicals, product name “Toughmer A-1070S”, MFR (230 ° C.) = 2.2 g / 10 min) is used, so as to except that each pellet was dry blends were prepared pellets of the thermoplastic resin composition of Comparative example 3 in the same manner as in experiment example 1. Next, by injection molding in the same manner as Experiment Example 1, to obtain a physical property measurement for the test piece of Comparative Example 3.

<Comparative example 4>
(C) As a compatibilizer, unmodified SEBS (manufactured by Asahi Kasei Chemicals Corporation, product name “Tuftec H1041”, MFR (230 ° C.) = 5 g / 10 min) was used. except that the pellets were dry blended, to prepare pellets of a thermoplastic resin composition of Comparative example 4 in the same manner as in experiment example 1. Next, by injection molding in the same manner as Experiment Example 1, to obtain a physical property measurement for the test piece of Comparative Example 4.

<Comparative Example 5>
As the polyolefin resin, a polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “NOVATEC MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as a twin-screw melt kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm). , L / D = 59), mixing at a kneading temperature of 210 ° C., an extrusion speed of 2.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded with a pelletizer The composition was cut to produce pellets of the thermoplastic resin composition of Comparative Example 5 (see Table 2). Next, by injection molding in the same manner as Experiment Example 1, to obtain a physical property measurement for the test piece of Comparative Example 5.

[2] Evaluation of thermoplastic resin composition (Experiment Examples 1 to 18 and Comparative Examples 1 to 5)
(1) using the experimental examples 1 to 18 and each physical property measurement for the test piece of Comparative Examples 1 to 5 obtained by the measurement above Charpy impact strength [1], Charpy impact strength in compliance with JIS K7111-1 Was measured. The results in Table 3, shown in FIG. 1 (Experimental Examples 1 to 4 and Comparative Examples 1 to 4) and 2 (experiment Examples 1-4 and Comparative Examples 1-4). In this Charpy impact strength measurement, a test piece having a notch (type A) was used, and the impact was measured by an edgewise test method at a temperature of 23 ° C.

(2) Bending using experimental examples 1 to 18 and each physical property measurement for the test piece of Comparative Examples 1 to 5 obtained by the measurement above elastic modulus [1], the measurement of flexural modulus in conformity with JIS K7171 Went. The results are shown in Table 3. This bending elastic modulus is measured at a speed of 2 mm from an action point (curvature radius 5 mm) arranged at the center between the fulcrums while supporting each test piece at two fulcrums (curvature radius 5 mm) with a distance (L) between the fulcrums of 64 mm. The measurement was performed by applying a load at / min.

(3) the Moruforuji observed above [2] fracture surface Experiment Example 2 for measuring physical properties test piece was subjected to measurement of the Charpy impact strength (1), a scanning electron microscope (manufactured by JEOL Ltd.), 5000 An image obtained by enlarging the image twice is shown in FIG.

[3] Effects Table 3 Experiment Examples 1 to 18, Comparative Examples 1 to 4 using the modified polypropylene or non-modified elastomer as the compatibilizer, flexural modulus was 1251～1386MPa, The Charpy impact strength was a low value of 1.4 to 4.2 kJ / m ² . In Comparative Example 5 in which the polyamide resin and the compatibilizer were not used, the flexural modulus was 1476 MPa, but the Charpy impact strength was a low value of 2.48 kJ / m ² .
In contrast, in Experiment Examples 1 to 18 was used modified elastomer as compatibilizer, flexural modulus is 710～1241MPa, Charpy impact strength is 6.4~86.3kJ / ^{m 2,} It was found that it has excellent rigidity and impact resistance.

In particular, as is clear from FIG. 1 and Table 3, it was confirmed that the impact resistance could be improved while maintaining sufficient rigidity by modifying the elastomer as the compatibilizer.
Specifically, the Charpy impact strength of Comparative Example 2 using the unmodified EPR as compatibilizer whereas was 2.7kJ / m ^2, Experiment Example 1 using the maleic anhydride-modified EPR The Charpy impact strength was 6.5 kJ / m ² , confirming a significant improvement in impact resistance. Also, Charpy impact strength of Comparative Example 3 using the unmodified EBR whereas was 4.2kJ / ^{m 2,} Charpy impact strength of experimental example 2 using maleic anhydride-modified EBR is 10.1kJ / M ² , confirming a significant improvement in impact resistance. Furthermore, while the Charpy impact strength of Comparative Example 4 using the unmodified SEBS was 2.8kJ / ^{m 2,} Charpy impact strength of experimental example 3 using the maleic anhydride-modified SEBS is 7 kJ / m ^2. It was confirmed that the impact resistance was greatly improved.

Further, as apparent from FIG. 2 and Table 3, it was confirmed that the impact resistance could be improved while maintaining sufficient rigidity by using a modified elastomer among the modified substances as a compatibilizing agent.
Specifically, the Charpy impact strength of Comparative Example 1 using the modified polypropylene as the compatibilizer whereas was 1.4kJ / m ^2, Charpy the experimental example 1-4 using the modified elastomer The impact strength was 6.5 to 10.1 kJ / m ² , confirming a significant improvement in impact resistance.

From the results of FIG. 3, it can be seen that the test piece of Experimental Example 2 and has a sea-island structure. It can be confirmed that most of the island phase (that is, the polyamide resin that is the dispersed phase) is uniformly finely dispersed with an average particle diameter of about 800 nm in the sea phase (that is, the polypropylene resin that is the mother phase). From this, it can be considered that both the impact resistance characteristics and the rigidity characteristics are effectively improved by this structure obtained by using a specific compatibilizer.

[4] Manufacture of a thermoplastic resin composition using a resin other than PA11 as a polyamide resin and preparation of test pieces (Note that the following Experimental Examples 19 to 47 are all reference examples).
<Experimental Example 19>
(1) Preparation of mixed resin (A) PA6 (nylon 6 resin, Ube Industries, Ltd., product name “1010X1”, melting point 225 ° C.) is used as a polyamide resin, and maleic anhydride modified as a compatibilizer (C) Using EBR (Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min), these pellets were dry blended so as to have the composition shown in Table 4, and then biaxial It is put into a melt kneading extruder (manufactured by Technobel Co., Ltd., screw diameter 15 mm, L / D = 59), and mixing is performed under conditions of kneading temperature 260 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rpm. Furthermore, the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 4 were put into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), and kneading temperature 260 ° C. , extrusion rate 2.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further thermoplastic resin composition of the experimental example 19 was cut to a thermoplastic resin composition extruded by using a pelletizer A pellet was prepared.
Then, the pellets of the thermoplastic resin composition of the experimental example 19 thus obtained, an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of a set temperature 260 ° C., mold temperature A test piece for measuring physical properties was injection molded under injection conditions of 60 ° C.

<Experimental Examples 20 to 24>
As shown in Table 4, using each (C) compatibilizer below, except that each pellet was dry-blended so that the composition shown in Table 4, Experiment Examples in the same manner as in Experimental Example 19 20-24 thermoplastic resin composition pellets were prepared. Next, by injection molding in the same manner as experimental example 19, to obtain a physical property test pieces for measuring the experimental examples 20 to 24.
(Compatibilizing agent used in the experimental example (C) of the details)
Experimental Example 20; maleic anhydride modified EBR (manufactured by Mitsui Chemicals, Inc., product name "TAFMER MA8510", MFR (230 ℃) = 5.0g / 10 min)
Experimental Example 21; maleic anhydride modified EBR (manufactured by Mitsui Chemicals, Inc., product name "TAFMER MH7010", MFR (230 ℃) = 1.8g / 10 min)
Experimental Example 22; maleic anhydride modified EBR (manufactured by Mitsui Chemicals, Inc., product name "TAFMER MH7020", MFR (230 ℃) = 1.5g / 10 min)
Experimental Example 23; maleic anhydride modified EBR (manufactured by Mitsui Chemicals, Inc., product name "TAFMER MH5040", MFR (230 ℃) = 1.1g / 10 min)
Experimental Example 24; maleic anhydride modified EOR (Dow Chemical Co., product name "AMPLIFY GR216", weight average molecular weight of 150,000, maleic anhydride-modified amount = 0.8 wt%)

<Comparative Example 6>
(A) PA6 (nylon 6 resin, manufactured by Ube Industries, product name “1010X1”, melting point 225 ° C.) as the polyamide resin, and (B) polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “ Novatec MA1B ”, weight average molecular weight 312,000, melting point 165 ° C., and after dry blending so as to have the composition shown in Table 4, twin-screw melt kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59), mixing at a kneading temperature of 260 ° C., an extrusion speed of 2.0 kg / hour, a screw rotation speed of 200 revolutions / minute, and further extruding the thermoplastic resin composition extruded using a pelletizer The pellet of the thermoplastic resin composition of the comparative example 6 was produced by cutting.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 6 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), and set temperature 260 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Experimental Example 25>
(1) Preparation of mixed resin (A) PA12 (nylon 12 resin, manufactured by Arkema Co., Ltd., product name “Rilsan AECN OTL”, melting point 174 to 178 ° C.) was used as a polyamide resin, and anhydrous as a compatibilizer (C) After dry blending these pellets using the maleic acid-modified EBR (Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) so as to have the composition shown in Table 5. And put into a twin-screw melt kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59), under conditions of kneading temperature 210 ° C., extrusion speed 2.0 kg / hour, screw rotation speed 200 rpm. Mixing was performed, and the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 5 were put into a biaxial melt kneading extruder (manufactured by Technobell, screw diameter 15 mm, L / D = 59), and kneading temperature 210 ° C. , extrusion rate 2.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further thermoplastic resin composition of the experimental example 25 was cut to a thermoplastic resin composition extruded by using a pelletizer A pellet was prepared.
Then, the pellets of the thermoplastic resin composition obtained experimental example 25, the injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of a preset temperature of 210 ° C., mold temperature A test piece for measuring physical properties was injection molded under injection conditions of 60 ° C.

<Experimental Example 26>
Each pellet so that the formulation shown in Table 5 except that the dry blend to prepare a pellet of the thermoplastic resin composition of the experimental example 26 in the same manner as in Experimental Example 25. Next, by injection molding in the same manner as experimental example 25 to obtain physical property measurement for test piece of Experimental Example 26.

<Comparative Example 7>
As a polyamide resin, PA12 (nylon 12 resin, manufactured by Arkema Co., Ltd., product name “Rilsan AECN OTL”, melting point: 174 to 178 ° C.) was mixed with a twin-screw melt kneading extruder (manufactured by Technobel, screw diameter 15 mm, L / D = 59), mixing at a kneading temperature of 210 ° C., an extrusion speed of 2.0 kg / hour, and a screw speed of 200 revolutions / minute, and further cutting the extruded thermoplastic resin composition using a pelletizer. Thus, pellets of the thermoplastic resin composition of Comparative Example 7 were produced (see Table 5). Next, by injection molding in the same manner as experimental example 25 to obtain physical property measurement for the test piece of Comparative Example 7.

<Experimental Example 27>
(1) Preparation of mixed resin (A) PA 610 (nylon 610 resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid Terra HS16”, melting point 222 ° C.) is used as a compatibilizing agent (C) and anhydrous. After dry blending these pellets using the maleic acid-modified EBR (Mitsui Chemicals Co., Ltd., product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) so as to have the composition shown in Table 6. , Put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 235 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 rpm Then, the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 6 were put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 235 ° C., extrusion rate 3.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further thermoplastic resin composition of cut experimental example 27 a thermoplastic resin composition extruded by using a pelletizer Article pellets were made.
Then, the pellets of the obtained thermoplastic resin composition of the experimental example 27, the injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of a preset temperature of 235 ° C., mold temperature A test piece for measuring physical properties was injection molded under injection conditions of 60 ° C.

<Experimental Example 28-32>
Each pellet so that the formulation shown in Table 6 except that the dry blend to prepare a pellet of the thermoplastic resin composition of the experimental example 28-32 In the same manner as experimental example 27. Next, by injection molding in the same manner as experimental example 27, to obtain a physical property test pieces for measuring the experimental examples 28-32.

<Comparative Example 8>
(A) PA610 as a polyamide resin (nylon 610 resin, manufactured by Daicel Evonik Co., Ltd., product name “Vestamid Terra HS16”, melting point 222 ° C.) and (B) a polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd.) , Product name “Novatech MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 6, followed by a biaxial melt kneading extruder (manufactured by Parker Corporation, screw) Thermoplastic extruded into a 25 mm diameter, L / D = 41), mixed at a kneading temperature of 235 ° C., an extrusion speed of 3.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded using a pelletizer The pellet of the thermoplastic resin composition of Comparative Example 8 was cut by cutting the resin composition. To prepare a door.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 8 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 235 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Experimental Example 33>
(1) Preparation of mixed resin (A) PA1010 (nylon 1010 resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid Terra DS16”, melting point 206 ° C.) is used as a compatibilizing agent (C) and anhydrous. After dry blending these pellets using the maleic acid-modified EBR (Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) so as to have the composition shown in Table 7. , Put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 250 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 rpm In addition, the mixed resin extruded using a pelletizer is cut to produce mixed resin pellets. It was.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. After dry blending with the mixed resin pellets and the composition shown in Table 7, the mixture was put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 250 ° C., extrusion rate 3.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further thermoplastic resin composition of the experimental example 33 was cut to a thermoplastic resin composition extruded by using a pelletizer Article pellets were made.
Then, the pellets of the thermoplastic resin composition obtained experimental example 33, the injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of the set temperature 250 ° C., mold temperature A test piece for measuring physical properties was injection molded under injection conditions of 60 ° C.

<Experimental Examples 34 to 38>
Each pellet so that the formulation shown in Table 7 except that the dry blend to prepare a pellet of the thermoplastic resin composition of the experimental example 34-38 In the same manner as experimental example 33. Next, by injection molding in the same manner as experimental example 33, to obtain a physical property test pieces for measuring the experimental examples 34 to 38.

<Comparative Example 9>
(A) PA1010 (nylon 1010 resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid Terra DS16”, melting point 206 ° C.) as the polyamide resin, and (B) polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd.) as the polyolefin resin , Product name “NOVATEC MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 7, followed by a twin-screw melt-kneading extruder (manufactured by Parker Corporation, screw) Thermoplastic extruded into a 25 mm diameter, L / D = 41), mixed at a kneading temperature of 250 ° C., an extrusion speed of 3.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded using a pelletizer The thermoplastic resin composition of Comparative Example 9 was cut by cutting the resin composition. To prepare a toilet.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 9 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), and set temperature 250 ° C., mold temperature 60 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Experimental Example 39>
(1) Preparation of mixed resin (A) PAMXD6 (nylon MXD6 resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name “Reny 6002”, melting point 243 ° C.) was used as a polyamide resin, and anhydrous as a compatibilizer (C) After using a maleic acid-modified EBR (Mitsui Chemicals Co., Ltd., product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min) and dry-blending these pellets to the formulation shown in Table 8 , Put into a twin-screw melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 265 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 rpm Then, the mixed resin extruded using a pelletizer was cut to produce mixed resin pellets.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. The obtained mixed resin pellets and dry blended so as to have the composition shown in Table 8 were put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 265 ° C., extrusion rate 3.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further thermoplastic resin composition of the experimental example 39 was cut to a thermoplastic resin composition extruded by using a pelletizer Article pellets were made.
Then, the pellets of the thermoplastic resin composition obtained experimental example 39, the injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of a preset temperature of 265 ° C., mold temperature A test piece for measuring physical properties was injection-molded under an injection condition of 90 ° C.

<Experimental Examples 40 to 44>
Each pellet so that the formulation shown in Table 8 except that the dry blend to prepare a pellet of the thermoplastic resin composition of the experimental example 40-44 In the same manner as experimental example 39. Next, by injection molding in the same manner as experimental example 39, to obtain a physical property test pieces for measuring the experimental examples 40 to 44.

<Comparative Example 10>
(A) PAMXD6 (nylon MXD6 resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name “Lenny 6002”, melting point 243 ° C.) as the polyamide resin, and (B) polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd.) , Product name “Novatech MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 8, followed by a twin-screw melt kneading extruder (manufactured by Parker Corporation, screw) Thermoplastic extruded into a 25 mm diameter, L / D = 41), mixed at a kneading temperature of 265 ° C., an extrusion speed of 3.0 kg / hour, and a screw speed of 200 revolutions / minute, and further extruded using a pelletizer The resin composition was cut and the thermoplastic resin composition of Comparative Example 10 was cut. The Tsu door was fabricated.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 10 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40-ton injection molding machine), and a set temperature of 265 ° C. and a mold temperature of 90 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

<Experimental Example 45>
(1) Preparation of mixed resin (A) PA10T (nylon 10T resin, manufactured by Daicel Evonik Co., Ltd., product name “Vestamid HT Plus M3000”, melting point 285 ° C.) was used as a polyamide resin, and as a compatibilizer (C), Using maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name “Tuffmer MH7020”, MFR (230 ° C.) = 1.5 g / 10 min), these pellets were dry blended so as to have the composition shown in Table 9. Thereafter, it is put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), kneading temperature 310 ° C., extrusion speed 3.0 kg / hour, screw rotation speed 200 revolutions / minute. Mixing is performed under the conditions, and the mixed resin extruded using a pelletizer is cut to produce mixed resin pellets. It was.

(2) Mixing step Next, polypropylene resin (homopolymer, manufactured by Nippon Polypro Co., Ltd., product name “Novatec MA1B”, weight average molecular weight 312,000, melting point 165 ° C.) is used as the polyolefin resin. After dry blending with the mixed resin pellets as shown in Table 9, the mixture was put into a biaxial melt kneading extruder (manufactured by Parker Corporation, screw diameter 25 mm, L / D = 41), and kneading temperature 310 ° C., extrusion rate 3.0 kg / time, and mixed and the conditions of a screw speed of 200 rev / min, further thermoplastic resin composition of the thermoplastic resin composition was cut experimental example 45 extruded using a pelletizer Article pellets were made.
Then, the pellets of the thermoplastic resin composition obtained experimental example 45, the injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. 40-ton injection molding machine) was charged into a hopper of a preset temperature of 310 ° C., mold temperature A test piece for measuring physical properties was injection-molded under an injection condition of 90 ° C.

<Experimental Example 46-47>
Each pellet so that the formulation shown in Table 9 except that the dry blend to prepare a pellet of the thermoplastic resin composition of the experimental example 46-47 In the same manner as experimental example 45. Next, by injection molding in the same manner as experimental example 45, to obtain a physical property test pieces for measuring the experimental examples 46-47.

<Comparative Example 11>
(A) PA10T (Nylon 10T resin, manufactured by Daicel-Evonik Co., Ltd., product name “Vestamid HT Plus M3000”, melting point 285 ° C.) as the polyamide resin, and (B) Polypropylene resin (Homopolymer, Nippon Polypro Co., Ltd.) as the polyolefin resin Manufactured, product name “Novatech MA1B”, weight average molecular weight 312,000, melting point 165 ° C., and dry blended so as to have the composition shown in Table 9, followed by a biaxial melt kneading extruder (manufactured by Parker Corporation, The screw diameter was 25 mm, L / D = 41), mixing was performed at a kneading temperature of 310 ° C., an extrusion speed of 3.0 kg / hour, a screw rotation speed of 200 revolutions / minute, and the heat extruded using a pelletizer The thermoplastic resin composition of Comparative Example 11 by cutting the plastic resin composition A pellet was prepared.
Thereafter, the obtained pellet of the thermoplastic resin composition of Comparative Example 11 was put into a hopper of an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., 40 ton injection molding machine), set temperature 310 ° C., mold temperature 90 A test piece for measuring physical properties was injection-molded under the injection condition of ° C.

[5] Evaluation of thermoplastic resin composition (Experiment Examples 19 to 47 and Comparative Examples 6 to 11)
Using experimental examples 19 to 47 and the physical property measurement for the test piece of Comparative Example 6 to 11 obtained in the above [4], in the same manner as in [2], the measurement of the Charpy impact strength, and flexural elasticity The rate was measured. The results are also shown in Tables 4-9.

[6] Effects Table 4 Experiment example 19 to 47, using PA6 as polyamide, in Comparative Example 6 was not used compatibilizer, flexural modulus was 2022MPa, Charpy impact strength Was as low as 2.3 kJ / m ² .
In contrast, using PA6 as polyamide, In Experiment Example 19 to 24 using the modified elastomer as the compatibilizer, a flexural modulus of 1325～1467MPa, Charpy impact strength 3.9~16.6kJ / M ² , which was found to be excellent in rigidity and impact resistance.

According to Table 5, in Comparative Example 7 where only PA12 was used as the polyamide and no polyolefin and no compatibilizer were used, the flexural modulus was 1340 MPa, but the Charpy impact strength was 2.8 kJ / m ² . It was a low value.
In contrast, using PA12 as polyamide, In Experiment Example 25-26 Using modified elastomer as the compatibilizer, a flexural modulus of 1253～1434MPa, Charpy impact strength 7.7~12.8kJ / M ² , which was found to be excellent in rigidity and impact resistance.

According to Table 6, in Comparative Example 8 in which PA610 was used as the polyamide and no compatibilizer was used, the flexural modulus was 1730 MPa, but the Charpy impact strength was as low as 2.1 kJ / m ^2. there were.
In contrast, using PA610 as polyamide, In Experiment Example 27 to 32 using the modified elastomer as the compatibilizer, a flexural modulus of 660～1390MPa, Charpy impact strength 5.4~40.0kJ / M ² , which was found to be excellent in rigidity and impact resistance.

According to Table 7, in Comparative Example 9 in which PA1010 was used as the polyamide and no compatibilizer was used, the flexural modulus was 1650 MPa, but the Charpy impact strength was as low as 1.1 kJ / m ^2. there were.
In contrast, using the PA1010 as polyamide, In Experiment Example 33 to 38 using the modified elastomer as the compatibilizer, a flexural modulus of 550～1350MPa, Charpy impact strength 2.1~40.0kJ / M ² , which was found to be excellent in rigidity and impact resistance.

According to Table 8, in Comparative Example 10 where PAMXD6 was used as the polyamide and no compatibilizer was used, the flexural modulus was 2270 MPa, but the Charpy impact strength was a low value of 1.1 kJ / m ^2. there were.
In contrast, using PAMXD6 as polyamide, In Experiment Example 39 to 44 using the modified elastomer as the compatibilizer, a flexural modulus of 820～2640MPa, Charpy impact strength 2.2~56.0kJ / M ² , which was found to be excellent in rigidity and impact resistance.

According to Table 9, in Comparative Example 11 in which PA10T was used as the polyamide and no compatibilizer was used, the flexural modulus was 1860 MPa, but the Charpy impact strength was as low as 1.1 kJ / m ^2. there were.
In contrast, using PA10T as polyamide, In Experiment Example 45-47 Using modified elastomer as the compatibilizer, a flexural modulus of 910～1620MPa, Charpy impact strength 2.1~5.0kJ / M ² , which was found to be excellent in rigidity and impact resistance.

  The foregoing examples are for illustrative purposes only and are not to be construed as limiting the invention. Although the invention has been described with reference to exemplary embodiments, it is to be understood that the language used in the description and illustration of the invention is illustrative and exemplary rather than limiting. As detailed herein, changes may be made in its form within the scope of the appended claims without departing from the scope or spirit of the invention. Although specific structures, materials and examples have been referred to in the detailed description of the invention herein, it is not intended to limit the invention to the disclosures presented herein, but rather, the invention is claimed. It covers all functionally equivalent structures, methods and uses within the scope of

Claims (3)

A thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
Obtained by melt-kneading a mixed resin in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin,
The thermoplastic resin composition, wherein the compatibilizer is a modified elastomer in which a reactive group capable of reacting with the polyamide resin is added to the elastomer.   2. The thermoplastic resin composition according to claim 1, wherein the elastomer is an olefin thermoplastic elastomer or a styrene thermoplastic elastomer made of a polymer of ethylene or propylene and an α-olefin having 3 to 8 carbon atoms. A method for producing a thermoplastic resin composition in which a polyamide resin is dispersed and contained in a polyolefin resin,
A mixing step in which a polyamide resin and a compatibilizer are melt-kneaded and a polyolefin resin are mixed and kneaded;
The method for producing a thermoplastic resin composition, wherein the compatibilizer is a modified elastomer in which a reactive group capable of reacting with the polyamide resin is added to the elastomer.